Compound, epoxy curing catalyst and method for producing compound

ABSTRACT

A novel compound suitable as an epoxy curing catalyst; an epoxy curing catalyst using the compound; and a method for producing the compound. A compound represented by formula (1) in which Xm+ represents an m valent counter cation, R1 represents an aromatic group which may have a substituent; R2 represents an alkylene group which may have a substituent; R3 represents a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfonic acid ester group, a phosphino group, a phosphinyl group, a phosphonic acid ester group or an organic group; m represents an integer of 1 or more; n represents an integer of 0-3; and R2 may bond with R1 to form a cyclic structure.

This application is the U.S. National Phase under 35 U.S.C. § 371 ofInternational Application PCT/JP2018/035772, filed Sep. 26, 2018,designating the U.S., and published in Japanese as WO 2019/065770 onApr. 4, 2019 which claims priority to Japanese Patent Application No.2017-191740, filed Sep. 29, 2017, the entire content of which isincorporated herein by reference.

PARTIES TO JOINT RESEARCH AGREEMENT

The present invention was made pursuant to a joint research agreementbetween Tokyo Ohka Kogyo Co., Ltd. and Daicel Corporation.

TECHNICAL FIELD

The present invention relates to a novel compound suitable as an epoxycuring catalyst, an epoxy curing catalyst using the compound, and amethod for producing the compound.

BACKGROUND ART

A curable composition including an epoxy compound, a curing agent, and acuring catalyst has widely been used in various applications such asadhesive applications, sealing applications of various electroniccomponents, and matrix formation applications of fiber-reinforcedcomposite materials. In such a curable composition, curability by acuring agent and a curing catalyst is required to be further improved(for example, Patent Document 1).

On the other hand, Patent Document 2 describes an imidazole compoundhaving a specific structure giving a metal surface treatment liquidhaving an excellent effect of suppressing migration or oxidation ofwiring surface.

-   Patent Document 1: Japanese Unexamined Patent Application,    Publication No. 2016-074890-   Patent Document 2: PCT International Publication No. WO2016/031928

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention

In view of the requirement of further improvement of curability of acurable composition including an epoxy compound of the above-mentionedconventional technology, the present invention has an object to providea novel compound suitable as an epoxy curing catalyst, an epoxy curingcatalyst using the compound, and a method for producing the compound.

Means for Solving the Problems

The present inventors have found that a novel compound including aplurality of residues exhibiting epoxy curability inside a molecule inthe same or different conditions can improve the curability of a curablecomposition including an epoxy compound (for example, improve heatresistance of an epoxy cured product) and is suitable as an epoxy curingcatalyst, and that when the compound includes a plurality of differentresidues exhibiting epoxy curability in different conditions, it canexhibit gradual epoxy curability during heating, and have completed thepresent invention.

A first aspect of the present invention is a compound represented by thefollowing formula (1).

(In the formula (1), X^(m+) represents an m-valent counter cation; R¹represents an optionally substituted aromatic group; R² represents anoptionally substituted alkylene group; R³ represents a halogen atom, ahydroxyl group, a mercapto group, a sulfide group, a silyl group, asilanol group, a nitro group, a nitroso group, a sulfonate group, aphosphino group, a phosphinyl group, a phosphonate group, or an organicgroup; m is an integer of 1 or more; n is an integer of 0 or more and 3or less; and R² may be bonded to R¹ to form a cyclic structure.)

A second aspect of the present invention is an epoxy curing catalystincluding the compound of the first aspect. A third aspect of thepresent invention is a method for producing the compound of the firstaspect, the method including producing the compound of the first aspectby neutralizing the compound represented by the formula (10) below, anda base capable of forming an m-valent counter cation X^(m+) in thepresence or absence of a solvent.

(In the formula (10), R¹ is an optionally substituted aromatic group; R²is an optionally substituted alkylene group; R³ is a halogen atom, ahydroxyl group, a mercapto group, a sulfide group, a silyl group, asilanol group, a nitro group, a nitroso group, a sulfonate group, aphosphino group, a phosphinyl group, a phosphonate group, or an organicgroup; n is an integer of 0 or more and 3 or less; and R² may be bondedto R¹ to form a cyclic structure.)

Effects of the Invention

The compound of the present invention is excellent in epoxy curability(for example, heat resistance of an epoxy cured product), and issuitable as an epoxy curing catalyst. Furthermore, the present inventioncan provide an epoxy curing catalyst using the compound, and a methodfor producing the compound.

PREFERRED MODE FOR CARRYING OUT THE INVENTION

Hereinafter, embodiments of the present invention will now be describedin detail, but the present invention is not necessarily limited to thefollowing embodiments and can be implemented with appropriatemodifications within the purpose of the present invention. Furthermore,in this specification, “ . . . to . . . ” represents “ . . . or more and. . . or less” unless otherwise notified.

<<Compound>>

The compound of the first aspect is represented by the following formula(1).

(In the formula (1), X^(m+) represents an m-valent counter cation; R¹represents an optionally substituted aromatic group; R² represents anoptionally substituted alkylene group; R³ represents a halogen atom, ahydroxyl group, a mercapto group, a sulfide group, a silyl group, asilanol group, a nitro group, a nitroso group, a sulfonate group, aphosphino group, a phosphinyl group, a phosphonate group, or an organicgroup; m is an integer of 1 or more; n is an integer of 0 or more and 3or less; and R² may be bonded to R¹ to form a cyclic structure.)

The m-valent counter cation X^(m+) is preferably an acyclic or cyclicnitrogen-containing aliphatic cation, a nitrogen-containing aromaticcation, or a metal cation. m is an integer of preferably 1 or more and 3or less, more preferably 1 or 2, and further preferably 1. Preferably,the above-listed acyclic or cyclic nitrogen-containing aliphatic cationis represented by any one of the following formulae (2) to (4) below.

(In the formula (2), R¹¹ to R¹⁴ each independently represent a hydrogenatom, an optionally substituted alkyl group, an optionally substitutedcycloalkyl group, an optionally substituted alkenyl group, an optionallysubstituted alkynyl group, an optionally substituted aryl group, anoptionally substituted aralkyl group, or an optionally substitutedheterocyclic group, and at least two selected from R¹¹ to R¹⁴ may linktogether to form a ring.)

In the formula (2), as the optionally substituted alkyl group, an alkylgroup having 1 or more and 30 or less carbon atoms is preferable.Specific examples of the optionally substituted alkyl group include amethyl group, an ethyl group, an n-propyl group, an n-butyl group, ann-hexyl group, an n-octyl group, an n-decyl group, an n-dodecyl group,an n-octadecyl group, an isopropyl group, an isobutyl group, a sec-butylgroup, a tert-butyl group, 1-ethylpentyl group, a trifluoromethyl group,a 2-ethyl hexyl group, a phenacyl group, a 1-naphthoylmethyl group, a2-naphthoylmethyl group, a 4-methylsulfanyl phenacyl group, a 4-phenylsulfanylphenacyl group, a 4-dimethylamino phenacyl group, a4-cyanophenacyl group, a 4-methylphenacyl group, a 2-methylphenacylgroup, a 3-fluorophenacyl group, a 3-trifluoromethylphenacyl group, a3-nitrophenacyl group, and the like. As the optionally substitutedcycloalkyl group, a cycloalkyl group having 5 or more and 30 or lesscarbon atoms is preferable. Specific examples of the optionallysubstituted cycloalkyl group include a cyclopentyl group, a cyclohexylgroup, and the like.

As the optionally substituted alkenyl group, an alkenyl group having 2or more and 10 or less carbon atoms is preferable. Specific examples ofthe optionally substituted alkenyl group include a vinyl group, an arylgroup, a styryl group, and the like. As the optionally substitutedalkynyl group, an alkynyl group having 2 or more and 10 or less carbonatoms is preferable. Specific examples of the optionally substitutedalkynyl group include an ethynyl group, a propynyl group, a propargylgroup, and the like. As the optionally substituted aryl group, an arylgroup having 6 or more and 30 or less carbon atoms is preferable.Specific examples of the optionally substituted aryl group include aphenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group,a 9-anthryl group, a 9-phenanthryl group, a 1-pyrenyl group, a5-naphthacenyl group, a 1-indenyl group, a 2-azulenyl group, a9-fluorenyl group, a terphenyl group, a quaterphenyl group, an o-tolylgroup, an m-tolyl group, a p-tolyl group, a xylyl group, ano-cumenylgroup, an m-cumenyl group, a p-cumenyl group, a mesityl group, apentalenyl group, a binaphthalenyl group, a ternaphthalenyl group, aquaternaphthalenyl group, a heptalenyl group, a biphenylenyl group, anindacenyl group, a fluoranthenyl group, an acenaphthylenyl group, anaceanthrylenyl group, a phenalenyl group, a fluorenyl group, an anthrylgroup, a bianthracenyl group, a teranthracenyl group, aquateranthracenyl group, an anthraquinolyl group, a phenanthryl group, atriphenylenyl group, a pyrenyl group, a chrysenyl group, a naphthacenylgroup, a pleiadenyl group, a picenyl group, a perylenyl group, apentaphenyl group, a pentacenyl group, a tetraphenylenyl group, ahexaphenyl group, a hexacenyl group, a rubicenyl group, a coronenylgroup, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group,a pyranthrenyl group, an ovalenyl group, and the like.

As the optionally substituted aralkyl, an aralkyl group having 7 or moreand 20 or less carbon atoms is preferable, and examples thereof includea benzyl group, a phenethyl group, an α-naphthyl methyl group, aβ-naphthyl methyl group, a 2-α-naphthyl ethyl group, a 2-β-naphthylethyl group, and the like. As the optionally substituted heterocyclicgroup, an aromatic or aliphatic heterocycle including a nitrogen atom,an oxygen atom, a sulfur atom, and a phosphorus atom is preferable.Specific examples of the heterocycle include a thienyl group, abenzo[b]thienyl group, a naphtho[2,3-b]thienyl group, a thianthrenylgroup, a furyl group, a pyranyl group, an isobenzofuranyl group, achromenyl group, a xanthenyl group, a phenoxathiinyl group, a2H-pyrrolyl group, a pyrrolyl group, an imidazolyl group, a pyrazolylgroup, a pyridyl group, a pyrazinyl group, a pyrimidinyl group, apyridazinyl group, an indolizinyl group, an isoindolyl group, a3H-indolyl group, an indolyl group, a 1H-indazolyl group, a purinylgroup, a 4H-quinolizinyl group, an isoquinolyl group, a quinolyl group,a phthalazinyl group, a naphthyridinyl group, a quinoxalinyl group, aquinazolinyl group, a cinnolinyl group, a pteridinyl group, a4aH-carbazolyl group, a carbazolyl group, a β-carbolinyl group, aphenanthridinyl group, an acridinyl group, a perimidinyl group, aphenanthrolinyl group, a phenazinyl group, a phenarsazinyl group, anisothiazolyl group, a phenothiazinyl group, an isoxazolyl group, afurazanyl group, a phenoxazinyl group, an isochromanyl group, achromanyl group, a pyrrolidinyl group, a pyrrolinyl group, animidazolidinyl group, an imidazolinyl group, a pyrazolidinyl group, apyrazolinyl group, a piperidyl group, a piperazinyl group, an indolinylgroup, an isoindolinyl group, a quinuclidinyl group, a morpholinylgroup, and a thioxanthryl group.

A hydrogen atom of the optionally substituted alkyl group, theoptionally substituted cycloalkyl group, the optionally substitutedalkenyl group, the optionally substituted alkynyl group, the optionallysubstituted aryl group, the optionally substituted aralkyl group, or theoptionally substituted heterocyclic group mentioned above may besubstituted with further the other substituent.

Examples of such a substituent may include a halogen atom (for example,a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom); acyano group; a nitro group; an alkoxy group (a methoxy group, an ethoxygroup, a tert-butoxy group, and the like); an aryloxy group (a phenoxygroup, a p-tolyloxy group, and the like); an organoxycarbonyl group (amethoxycarbonyl group, a butoxycarbonyl group, a phenoxylcarbonyl group,a vinyloxycarbonyl group, and aryloxycarbonyl, group, and the like); anacyloxy group (an acetoxy group, a propionyloxy group, a benzoyl oxygroup, and the like); an acyl group (an acetyl group, a benzoyl group,an isobutyryl group, an acryloyl group, a methacryloyl group, amethoxalyl group, and the like); an alkylsulfanyl group (amethylsulfanyl group, a tert-butylsulfanyl group, and the like); anarylsulfanyl group (a phenylsulfanyl group, a p-tolylsulfanyl group, andthe like); an alkyl amino group (a methyl amino group, a cyclohexylamino group, and the like); a diakyl amino group (a dimethyl aminogroup, a diethyl amino group, a morpholino group, a piperidino group,and the like); an aryl amino group (a phenyl amino group, a p-tolylamino group, and the like); an alkyl group (a methyl group, an ethylgroup, a tert-butyl group, a dodecyl group, and the like); an aryl group(a phenyl group, a p-tolyl group, a xylyl group, a cumenyl group, anaphthyl group, an anthryl group, a phenanthryl group, and the like); ahydroxy group; a carboxy group; a sulfonamide group; a formyl group; amercapto group; a sulfo group; a mesyl group; a p-toluenesulfonyl group;an amino group; a nitroso group; a trifluoromethyl group, atrichloromethyl group; a trimethylsilyl group; a phosphinico group; aphosphono group; an alkyl sulfonyl group; an aryl sulfonyl group; atrialkyl ammonium group; a dimethylsulfoniumyl group; atriphenylphenancylphosphoniumyl group, and the like.

In the formula (2), when at least two selected from R¹¹ to R¹⁴ arebonded to each other to form a ring, examples of the linking groupinclude an alkylene group, a cycloalkylene group or a divalent groupobtained by bonding thereof. The number of carbon atoms of the linkinggroup is preferably 1 or more and 10 or less. The ring formed of atleast two selected from R¹¹ to R¹⁴ may include a ring-forming atoms andan oxygen atom.(R²¹)₂N⁺═C(NR²² ₂)₂  (3)(In the formula (3), R²¹ each independently represents a hydrogen atom,an alkyl group or a cycloalkyl group, R²² each independently representsa hydrogen atom, an alkyl group, a cycloalkyl group, a —C(═NR²³)—NR²³ ₂(three NR²³ each independently represents a hydrogen atom, an alkylgroup, or a cycloalkyl group), or ═C(—NR²⁴ ₂)₂ (four R²⁴ eachindependently represents a hydrogen atom or an organic group).)

As the alkyl group in R²¹ to R²³, an alkyl group having 1 or more and 10or less carbon atoms is preferable. Specific examples of the alkyl groupinclude a methyl group, an ethyl group, a propyl group, a butyl group, ahexyl group, an octyl group, a decyl group, a dodecyl group, anoctadecyl group, an isopropyl group, an isobutyl group, a sec-butylgroup, a tert-butyl group, a 1-ethylpentyl group, and the like. As thecycloalkyl group in R²¹ to R²³, a cycloalkyl group having 5 or more and30 or less carbon atoms is preferable. Specific examples of thecycloalkyl group include a cyclopentyl group, a cyclohexyl group, andthe like. Examples of the organic group for R²⁴ include an alkyl group,a cycloalkyl group, an aralkyl group, an aryl group, and the like.Examples of cations represented by the formula (3) include1,2-diisopropyl-3-[bis(dimethylamino)methylene]guanidinium cation,1-methylbiguanidium cation, 1-n-butylbiguanidium cation, 1-(2-ethylhexyl)biguanidium cation, 1-n-octadecylbiguanidium cation,1,1-dimethylbiguanidium cation, 1,1-diethylbiguanidium cation, 1-cyclohexyl biguanidium cation, 2-ethyl-1,1,3,3-tetramethylguanidinium cation,1-benzylguanidinium cation, 1,3-dibenzylguanidinium cation,1-benzyl-2,3-dimethylguanidinium cation, 1-phenylguanidinium cation, andthe like. Among these cations,1,2-diisopropyl-3-[bis(dimethylamino)methylene]guanidinium ispreferable.

(In the formula (4), R³¹ each independently represents a hydrogen atomor an organic group, and s represents an integer of 2 or more and 6 orless.)

Examples of the organic group for R³¹ include an alkyl group, acycloalkyl group, an aralkyl group, an aryl group, and the like. Thealkyl group above, the cycloalkyl group above, the aralkyl group above,and the aryl group above may have a substituent, respectively. Examplesof the substituent may include a halogen atom (for example, a fluorineatom, a chlorine atom, a bromine atom, and an iodine atom); a cyanogroup; a nitro group; an alkoxy group (a methoxy group, an ethoxy group,a tert-butoxy group, and the like); an aryloxy group (a phenoxy group, ap-tolyloxy group, and the like); an organoxycarbonyl group (amethoxycarbonyl group, a butoxycarbonyl group, a phenoxylcarbonyl group,a vinyloxycarbonyl group, and aryloxycarbonyl, group, and the like); anacyloxy group (an acetoxy group, a propionyloxy group, a benzoyl oxygroup, and the like); an acyl group (an acetyl group, a benzoyl group,an isobutyryl group, an acryloyl group, a methacryloyl group, amethoxalyl group, and the like); an alkylsulfanyl group (amethylsulfanyl group, a tert-butylsulfanyl group, and the like); anarylsulfanyl group (a phenylsulfanyl group, a p-tolylsulfanyl group, andthe like); an alkyl amino group (a methyl amino group, a cyclohexylamino group, and the like); a diakyl amino group (a dimethyl aminogroup, a diethyl amino group, a morpholino group, a piperidino group,and the like); an aryl amino group (a phenyl amino group, a p-tolylamino group, and the like); an alkyl group (a methyl group, an ethylgroup, a tert-butyl group, a dodecyl group, and the like); an aryl group(a phenyl group, a p-tolyl group, a xylyl group, a cumenyl group, anaphthyl group, an anthryl group, a phenanthryl group, and the like); ahydroxy group; a carboxy group; a sulfonamide group; a formyl group; amercapto group; a sulfo group; a mesyl group; a p-toluenesulfonyl group;an amino group; a nitroso group; a trifluoromethyl group, atrichloromethyl group; a trimethylsilyl group; a phosphinico group; aphosphono group; an alkyl sulfonyl group; an aryl sulfonyl group; atrialkyl ammonium group; a dimethylsulfoniumyl group; atriphenylphenancylphosphoniumyl group, and the like. s is an integer ofpreferably 3 or more and 5 or less, and more preferably 3 or 4.

As the nitrogen-containing aromatic cation of the counter cation X^(m+),the cation represented by any one of the following formulae (5) to (13)below is preferable.

(In the formula, R^(H) each independently represents a hydrogen atom oran alkyl group; R⁴¹, R⁴³, R⁴⁵, R⁴⁶, R⁴⁷, R⁴⁸, R⁵⁰, R⁵¹, and R⁵² eachindependently represents a hydrogen atom, a halogen atom, a cyano group,a nitro group, an alkyl group, a cycloalkyl group, an alkenyl group, oran alkynyl group; R⁴², R⁴⁴, and R⁴⁹ each independently represents ahydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, analkenyl group, or an alkynyl group. R⁴¹ to R⁵² each independently may besubstituted with a halogen atom, a cyan group, or a nitro group; R⁴¹ andR⁴² may be bonded to each other to form a ring; at least two R⁴¹s may bebonded to each other to form a ring; R⁴³ and R⁴⁴ may be bonded to eachother to form a ring; two R⁴³s may be bonded to each other to form aring; at least two R⁴⁵s may be bonded to each other to form a ring; atleast two R⁴⁶s may be bonded to each other to form a ring; at least twoR⁴⁷s may be bonded to each other to form a ring; R⁴⁸ and R⁴⁹ may bebonded to each other to form a ring; at least two R⁴⁸s may be bonded toeach other to form a ring; at least two R⁵⁰s may be bonded to each otherto form a ring; at least two R⁵¹s may be bonded to each other to form aring; at least two R⁵²s may be bonded to each other to form a ring.)

Examples of the halogen atom as R⁴¹ to R⁵² include a fluorine atom, achlorine atom, a bromine atom, or an iodine atom. The alkyl group forR^(H), and R⁴¹ to R⁵² may be a linear alkyl group or a branched alkylgroup. The number of carbon atoms of the alkyl group is not particularlylimited, but the number of carbon atoms of the alkyl group is preferably1 or more and 20 or less, more preferably 1 or more and 10 or less, andfurther preferably 1 or more and 5 or less. Specific examples of thealkyl group for R^(H), and R⁴¹ to R⁵² include a methyl group, an ethylgroup, an n-propyl group, an isopropyl group, an n-butyl group, anisobutyl group, an sec-butyl group, a tert-butyl group, an n-pentylgroup, an isopentyl group, a tert-pentyl group, an n-hexyl group, ann-heptyl group, an n-octyl group, a 2-ethyl-n-hexyl group, an n-nonylgroup, an n-decyl group, an n-undecyl group, an n-dodecyl group, ann-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, ann-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, ann-nonadecyl group, and an n-icosyl group.

The cycloalkyl group for R⁴¹ to R⁵² is preferably a cycloalkyl grouphaving 5 or more and 30 or less carbon atoms. Specific examples of thecycloalkyl group include a cyclopentyl group, a cyclohexyl group, andthe like. The alkenyl group for R⁴¹ to R⁵² is preferably an alkenylgroup having 2 or more and 10 or less carbon atoms. Specific examples ofthe alkenyl group include a vinyl group, an aryl group, a styryl group,and the like. The alkynyl group for R⁴¹ to R⁵² is preferably an alkynylgroup having 2 or more and 10 or less carbon atoms. Specific examples ofthe alkynyl group include an ethynyl group, a propynyl group, apropargyl group, and the like.

When m is an integer of 2 or more, the acyclic or cyclicnitrogen-containing aliphatic cation of the m-valent counter cationX^(m+) is preferably a cation represented by any one of the followingformulae (14) to (16) below.

(In the above formula, R^(H) each independently represents a hydrogenatom or an alkyl group; R⁵³ and R⁵⁵ each independently an alkyl group ora cycloalkyl group; R⁵⁴ represents an alkylene group, a cycloalkylenegroup or a divalent group obtained by bonding thereof; R⁵⁶ represents analkylene group; R⁵³ to R⁵⁶ each independently may be substituted with ahalogen atom, a cyano group or a nitro group; at least two R⁵³s may bebonded to each other to form a ring; R⁵³ and R⁵⁴ may be bonded to eachother to form a ring; two R⁵⁵s may be bonded to each other to form aring.)

Specific examples and preferable examples of R^(H) include the samespecific examples and preferable examples mentioned above. Examples ofthe alkyl group for R^(H) and R⁵³ to R⁵⁵ include the same alkyl groupsas those of the specific examples and preferable examples mentionedabove as the alkyl group for R^(H) and R⁴¹ to R⁵². The cycloalkyl groupfor R⁵³ to R⁵⁵ includes the same cycloalkyl groups as those of thespecific examples and preferable examples mentioned above as thecycloalkyl group for R⁴¹ to R⁵². The alkylene group for R⁵⁶ includes analkylene group having 1 or more and 5 or less carbon atoms. Examples ofthe alkylene group include a methylene group, an ethylene group, apropylene group, a butylene group, and the like.

When m is an integer of 2 or more, examples of the nitrogen-containingaromatic cation as the m-valent counter cation X^(m+) include cations ofdivalent or more having a 2,2-bipyridinium skeleton, a 3,3-bipyridiniumskeleton, a 4,4-bipyridinium skeleton, a 2,2-bipyrazinium skeleton, a4,4-biquinolinium skeleton, a 4,4-biisoquinolinium skeleton, a4-[2-(4-pyridinium)vinyl]pyridinium skeleton, or a4-[4-(4-pyridinium)phenyl]pyridinium skeleton in the molecule.

The metal cation as the counter cation X^(m+) is preferably cations ofmetal atoms selected from the group consisting of a typical metalelement, a transition metal element, and a semimetal element, or cationsof an atomic group including the above-mentioned metal atoms. Examplesof the above typical metal element include alkali metal elements (metalelements including elements belonging to Group 1 excluding hydrogen, forexample, sodium and potassium), alkali earth metal element (metalelements including elements belonging to Group 2, for example,magnesium), metal elements including elements belonging to Group 12 (forexample, zinc), metal elements including elements belonging to Group 13excluding boron (for example, aluminum), metal elements includingelements belonging to Group 14 excluding carbon and silicon (forexample, tin), metal elements including elements belonging to Group 15excluding nitrogen, phosphorus, and arsenic (for example, antimony), andmetal elements including elements belonging to Group 16 excludingoxygen, sulfur, selenium, and tellurium (for example, polonium).Examples of the above transition metal element include elementsincluding elements belonging to Groups 3 to 11 (for example, hafnium).Examples of the above semimetal element include elements such as boron,silicon, arsenic, selenium, and tellurium. Examples of cations of theatomic group including the above metal atoms include the atomic groupincluding both a metal atom and a nonmetal atom, and the like. Specificexamples thereof include [ZrO]²⁺, [(C₂H₅O)Al]²⁺,[(n-C₄H₉)₂Sn—O—Sn(n-C₄H₉)₂]²⁺, and the like.

In the formula (1), R¹ represents an optionally substituted aromaticgroup. The optionally substituted aromatic group may be either anoptionally substituted aromatic hydrocarbon group or an optionallysubstituted aromatic heterocyclic group.

The type of the aromatic hydrocarbon group is not particularly limitedas long as it does not interfere with the object of the presentinvention. The aromatic hydrocarbon group may be a monocyclic aromaticgroup, may be formed by condensation of two or more aromatic hydrocarbongroups, or may be formed by bonding of two or more aromatic hydrocarbongroups through a single bond. The aromatic hydrocarbon group ispreferably a phenyl group, a naphthyl group, a biphenylyl group, ananthryl group, and a phenanthrenyl group.

The type of the aromatic heterocyclic group is not particularly limitedas long as it does not interfere with the object of the presentinvention. The aromatic heterocyclic group may be either a monocyclicgroup or a polycyclic group. The aromatic heterocyclic group ispreferably a pyridyl group, a furyl group, a thienyl group, animidazolyl group, a pyrazolyl group, an oxazolyl group, a thiazolylgroup, an isoxazolyl group, an isothiazolyl group, a benzoxazolyl group,a benzothiazolyl group, and a benzimidazolyl group.

Examples of the substituent, which a phenyl group, a polycyclic aromatichydrocarbon group, or an aromatic heterocyclic group may have, include ahalogen atom, a hydroxyl group, a mercapto group, a sulfide group, asilyl group, a silanol group, a nitro group, a nitroso group, a sulfinogroup, a sulfo group, a sulfonate group, a phosphino group, a phosphinylgroup, a phosphono group, a phosphonate group, an amino group, anammonio group, and an organic group. When the phenyl group, thepolycyclic aromatic hydrocarbon group, or the aromatic heterocyclicgroup have plural substituents, the plural substituents may be the sameor different.

When the substituent, which the aromatic group has, is an organic group,examples of the organic group include an alkyl group, an alkenyl group,a cycloalkyl group, a cycloalkenyl group, an aryl group, an aralkylgroup, or the like. This organic group may have a bond or a substituent,other than a hydrocarbon group such as a heteroatom, in the organicgroup. This organic group may be either linear, branched, or cyclic.This organic group is usually monovalent, but can be a divalent orhigher polyvalent organic group when forming a cyclic structure.

When the aromatic group has a substituent on neighboring carbon atoms,two substituents bonded on neighboring carbon atoms may be bonded toform a cyclic structure. Examples of the cyclic structure include analiphatic hydrocarbon ring, and an aliphatic ring having a heteroatom.

When the substituent, which the aromatic group has, is an organic group,the bond included in the organic group is not particularly limited, aslong as it does not impair the effect of the present invention; and theorganic group may include a bond having a heteroatom such as an oxygenatom, a nitrogen atom, or a silicon atom. Specific examples of thebonded containing a heteroatom include, an ether bond, a thioether bond,a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, anamino bond (—NR^(A)—: R^(A) represents a hydrogen atom or a monovalentorganic group), a urethane bond, an imino bond (—N═C(—R^(B))—,—C(═NR^(B))—: R^(B) represents a hydrogen atom or a monovalent organicgroup), a carbonate bond, a sulfonyl bond, a sulfinyl bond, an azo bond,and the like.

From the viewpoint of heat resistance of the imidazole compoundrepresented by the formula (1), the bond containing a heteroatom, whichan organic group may have, is preferably an ether bond, a thioetherbond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amidebond, an amino bond (—NR^(A)—: R^(A) R represents a hydrogen atom or amonovalent organic group), an urethane bond, an imino bond(—N═C(—R^(B))—, —C(═NR^(B))—: R^(B) represents a hydrogen atom or amonovalent organic group), a carbonate bond, a sulfonyl bond, and asulfinyl bond.

When the organic group is a substituent other than the hydrocarbongroup, the type of substituents other than the hydrocarbon group is notparticularly limited as long as it does not interfere with the object ofthe present invention. Specific examples of the substituent other thanthe hydrocarbon group include a halogen atom, a hydroxyl group, amercapto group, a sulfide group, a cyano group, an isocyano group, acyanate group, an isocyanate group, a thiocyanate group, anisothiocyanate group, an silyl group, an silanol group, an alkoxy group,an alkoxycarbonyl group, an amino group, a monoalkylamino group, adialkylamino group, a monoarylamino group, a diarylamino group, acarbamoyl group, a thiocarbamoyl group, a nitro group, a nitroso group,a carboxylate group, an acyl group, an acyloxy group, a sulfino group, asulfonate group, a phosphino group, a phosphinyl group, a phosphonategroup, an alkyl ether group, an alkenyl ether group, an alkyl thioethergroup, an alkenyl thioether group, an aryl ether group, an arylthioether group, and the like. The hydrogen atom included in thesubstituent mentioned above may be substituted with a hydrocarbon group.The hydrocarbon group included in the substituent mentioned above may beeither linear, branched, or cyclic.

The substituent, which a phenyl group, a polycyclic aromatic hydrocarbongroup, or an aromatic heterocyclic group has, is preferably an alkylgroup having 1 or more and 12 or less carbon atoms, an aryl group having1 or more and 12 or less carbon atoms, an alkoxy group having 1 or moreand 12 or less carbon atoms, an aryloxy group having 1 or more and 12 orless carbon atoms, an arylamino group having 1 or more and 12 or lesscarbon atoms, and a halogen atom.

As R¹, a phenyl group, a furyl group, and a thienyl group, each of whichis optionally substituted, are preferable because a compound representedby formula (1) can be synthesized inexpensively and easily and thesolubility of the compound in water or an organic solvent is good.

In the formula (1), R² is an optionally substituted alkylene group. Thesubstituent, which an alkylene group may have, is not particularlylimited, as long as it does not interfere with the object of the presentinvention. Specific examples of the substituent, which an alkylene groupmay have, include a hydroxyl group, an alkoxy group, an amino group, acyano group, a halogen atom, and the like. The alkylene group may beeither a linear alkylene group or a branched alkylene group, and ispreferably a linear alkylene group. The number of carbon atoms of thealkylene group is not particularly limited, but is preferably 1 or moreand 20 or less, preferably 1 or more and 10 or less, and more preferably1 or more and 5 or less. Note here that the number of carbon atoms of analkylene group does not include the number of substituent carbon atomsbonded to the alkylene group.

The alkoxy group as the substituent bonded to the alkylene group may beeither a linear alkoxy group or a branched alkoxy group. The number ofcarbon atoms of the alkoxy group as the substituent is not particularlylimited, but is preferably 1 or more and 10 or less, more preferably 1or more and 6 or less, and particularly preferably 1 or more and 3 orless.

The amino group as the substituent bonded to the alkylene group may be amonoalkylamino group or a dialkylamino group. The alkyl group includedin the monoalkylamino group or dialkylamino group may be either a linearalkyl group or a branched alkyl group. The number of carbon atoms of thealkyl group included in the monoalkylamino group or dialkylamino groupis not particularly limited, but is preferably 1 or more and 10 or less,more preferably 1 or more and 6 or less, and particularly preferably 1or more and 3 or less.

Specific examples of the alkylene group suitable as R² include amethylene group, an ethane-1,2-diyl group, an n-propane-1,3-diyl group,an n-propane-2,2-diyl group, an n-butane-1,4-diyl group, ann-pentane-1,5-diyl group, an n-hexane-1,6-diyl group, ann-heptane-1,7-diyl group, an n-octane-1,8-diyl group, ann-nonane-1,9-diyl group, an n-decane-1,10-diyl group, ann-undecane-1,11-diyl group, an n-dodecane-1,12-diyl group, ann-tridecane-1,13-diyl group, an n-tetradecane-1,14-diyl group, ann-pentadecane-1,15-diyl group, an n-hexadecane-1,16-diyl group, ann-heptadecane-1,17-diyl group, an n-octadecane-1,18-diyl group, ann-nonadecane-1,19-diyl group, and an n-icosane-1,20-diyl group.

R³ represents a halogen atom, a hydroxyl group, a mercapto group, asulfide group, a silyl group, a silanol group, a nitro group, a nitrosogroup, a sulfonate group, a phosphino group, a phosphinyl group, aphosphonate group, or an organic group; and n is an integer of 0 or moreand 3 or less. When n is an integer of 2 to 3, a plurality of R³ may bethe same or different.

When R³ is an organic group, the organic group is the same as an organicgroup, which an aromatic group may have as a substituent, as for R¹.

When R³ is an organic group, the organic group is preferably an alkylgroup, an aromatic hydrocarbon group, and an aromatic heterocyclicgroup. The alkyl group is preferably a linear or branched alkyl grouphaving 1 or more and 8 or less carbon atoms, and more preferably amethyl group, an ethyl group, an n-propyl group, and an isopropyl group.The aromatic hydrocarbon group is preferably a phenyl group, a naphthylgroup, a biphenylyl group, an anthryl group, and a phenanthrenyl group,more preferably a phenyl group and a naphthyl group, and particularlypreferably a phenyl group. The aromatic heterocyclic group is preferablya pyridyl group, a furyl group, a thienyl group, an imidazolyl group, apyrazolyl group, an oxazolyl group, a thiazolyl group, an isoxazolylgroup, an isothiazolyl group, a benzoxazolyl group, a benzothiazolylgroup, and a benzimidazolyl group, and more preferably a furyl group anda thienyl group.

When R³ is an alkyl group, the position of the alkyl group bonding on animidazole ring is preferably any one of 2-, 4-, and 5-positions, andmore preferably 2-position. When R³ is an aromatic hydrocarbon group andan aromatic heterocyclic group, the position of these groups bonding onimidazole is preferably 2-position.

Among the compounds represented by the above-mentioned formula (1), fromthe viewpoint that a compound can be synthesized inexpensively andeasily and the solubility of the compound in water or an organic solventis good, the compound is preferably a compound represented by thefollowing formula (1-1), and more preferably a compound represented bythe formula (1-1) wherein R² is a methylene group.

(In the formula (1-1), X, R², R³, m and n are the same as those definedin the formula (1); and R⁴, R⁵, R⁶, R⁷, and R⁸ are each independently ahydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, asulfide group, a silyl group, a silanol group, a nitro group, a nitrosogroup, a sulfino group, a sulfo group, a sulfonate group, a phosphinogroup, a phosphinyl group, a phosphono group, a phosphonate group, anamino group, an ammonio group, or an organic group, wherein at least oneof R⁴, R⁵, R⁶, R⁷, and R⁸ is a group other than a hydrogen atom. Atleast two of R⁴, R⁵, R⁶, R⁷, and R⁸ may be bonded to each other to forma cyclic structure. R² and R⁶ may be bonded to each other to form acyclic structure.)

When R⁴, R⁵, R⁶, R⁷, and R⁸ are organic groups, the organic groups arethe same as an organic group, which R⁸ in the formula (1) has as asubstituent. R⁴, R⁵, R⁶, and R⁷ are preferably a hydrogen atom in viewof solubility of the above compound in solvent.

Among these, at least one of R⁴, R⁵, R⁶, R⁷, and R⁸ is preferably thefollowing substituent. Particularly preferably, R⁸ is the followingsubstituent. When R⁸ is the following substituent, R⁴, R⁵, R⁶, and R⁷are preferably a hydrogen atom.

—O—R⁹

(R⁹ is a hydrogen atom or an organic group.)

When R⁹ is an organic group, the organic group is the same as an organicgroup, which R¹ in the formula (1) has as a substituent. R⁹ ispreferably an alkyl group, more preferably, an alkyl group having 1 ormore and 8 or less carbon atoms, particularly preferably an alkyl grouphaving 1 or more and 3 or less carbon atoms, and most preferably amethyl group.

Among the compounds represented by the formula (1-1) mentioned above, acompound represented by the following formula (1-1-1) is preferable.

(In the formula (1-1-1), X, R³, R⁴, R⁵, R⁶, R⁷, and R⁸, m and n are thesame as those in the formula (1) except that at least one of R⁴, R⁵, R⁶,R⁷, and R⁸ is a group other than a hydrogen atom.)

Among the compounds represented by the formula (1-1-1), at least one ofR⁴, R⁵, R⁶, R⁷, and R⁸ is preferably represented by the above-mentioned—O—R⁹; and R⁸ is particularly preferably a group represented by —O— R⁹.When R⁸ is a group represented by —O— R⁹, R⁴, R⁵, R⁶, and R⁷ arepreferably hydrogen atoms.

Suitable specific examples of the compound represented by the formula(1) include the following.

<<Applications of Use>>

The compound represented by the above formula (1) according to the firstaspect can be used as an epoxy curing catalyst. The epoxy curingcatalyst according to the second aspect includes the compoundrepresented by the above formula (1) according to the first aspect. Itis preferable that the compound represented by the above formula (1) andthe epoxy compound are mixed by, for example, a stirrer to prepare acurable composition. Temperature and time for curing the above-mentionedcurable composition are not particularly limited as long as curingsufficiently progresses. For example, a curable composition is cured atabout 100° C. or more and 200° C. or less for 3 minutes or more and 10minutes or less. The above-mentioned curable composition can be cured ata low temperature, but it may also be cured at a high temperature. Thecontent of the compound represented by the above formula (1) in theabove-mentioned composition is not particularly limited. The content ofthe compound represented by the above formula (1) in the above-mentionedcomposition is, for example, preferably 0.01% by mass or more and 80% bymass or less, more preferably 0.1% by mass or more and 40% by mass orless, further preferably 0.5% by mass or more and 30% by mass or less,and particularly preferably 1% by mass or more and 15% by mass or lesswith respect to the entire composition (excluding a solvent). Theabove-mentioned composition may contain various additives as necessary.Examples of the additives include a coloring agent, a dispersing agent,a sensitizer, a curing accelerator, a filler, an adhesion promoter, anantioxidant, an ultraviolet absorber, an aggregation inhibitor, athermal polymerization inhibitor, an antifoaming agent, a surfactant,and the like.

The epoxy compound cured by the compound of the first aspect is notparticularly limited as long as it is a compound including an epoxygroup. The epoxy compound can be selected from various compounds havingan epoxy group conventionally blended in the curable composition. Theepoxy compound may be a non-polymer low-molecular weight compound havingan epoxy group or a polymer having an epoxy group. Hereinafter, withrespect to the epoxy compound, a non-polymer having an epoxy group and apolymer having an epoxy group are described sequentially.

(Non-Polymer Having an Epoxy Group)

A non-polymer having an epoxy group can be appropriately selected fromvarious non-polymer type epoxy compounds which have conventionally beenblended in a curable composition. Suitable examples of the epoxycompound include difunctional epoxy resin such as bisphenol A type epoxyresin, bisphenol F type epoxy resin, bisphenol S type epoxy resin,bisphenol AD type epoxy resin, naphthalene type epoxy resin, andbiphenyl type epoxy resin; glycidyl ester type epoxy resin such as dimeracid glycidyl ester and triglycidyl ester; glycidyl amine type epoxyresin such as tetraglycidyl aminodiphenylmethane,triglycidyl-p-aminophenol, tetraglycidyl metaxylylenediamine, andtetraglycidyl bisaminomethylcyclohexane; heterocyclic epoxy resin suchas triglycidyl isocyanurate; trifunctional epoxy resin such asphloroglucinol triglycidylether, trihydroxybiphenyl triglycidylether,trihydroxyphenylmethane triglycidylether, glycerin triglycidylether,2-[4-(2,3-epoxypropoxy)phenyl-2-[4-[1,1-bis[4-(2,3-epoxypropxy)phenyl]ethyl]phenyl]propane,and1,3-bis[4-[1-[4-(2,3-epoxypropoxy)phenyl]-1-[4-[1-[4-(2,3-epoxypropoxy)phenyl]-1-methylethyl]phenyl]ethyl]phenoxy]-2-propanol;and tetrafunctional epoxy resin such as tetrahydroxyphenylethanetetraglycidylether, tetraglycidyl benzophenone, bisresorcinoltetraglycidylether, and tetraglycidoxybiphenyl.

From the viewpoint that a cured product formed using a curablecomposition is excellent in its mechanical property, an aliphatic epoxycompound that does not include an aromatic group is also preferable.Among the aliphatic epoxy compounds, from the viewpoint of providing acured product having excellent transparency and hardness, an aliphaticepoxy compound having an alicyclic epoxy group is preferable. Specificexamples of the aliphatic epoxy compound having an alicyclic epoxy groupinclude2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-meta-dioxane,bis(3,4-epoxycyclohexylmethyl)adipate,bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate,3,4-epoxy-6-methylcyclohexyl-3′,4′-epoxy-6′-methylcyclohexanecarboxylate, ε-caprolactone-modified3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexane carboxylate,trimethylcaprolactone-modified3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexane carboxylate,β-methyl-δ-valerolactone-modified3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexane carboxylate,methylenebis(3,4-epoxycyclohexane), di(3,4-epoxycyclohexylmethyl)etherof ethylene glycol, ethylenebis(3,4-epoxycyclohexane carboxylate),dioctyl epoxycyclohexahydrophthalate, di-2-ethylhexylepoxycyclohexahydrophthalate, an epoxy resin having a tricyclodeceneoxide group, and the like.

(Polymer Having an Epoxy Group)

A polymer having an epoxy group may be a polymer obtained bypolymerizing a monomer having an epoxy group or a monomer mixtureincluding a monomer having an epoxy group or a polymer in which an epoxygroup is introduced into a polymer having a functional group havingreactivity, for example, a hydroxyl group, a carboxy group, an aminogroup, and the like, using a compound having an epoxy group, forexample, epichlorohydrin. Furthermore, partial oxide of a polymer havingan unsaturated aliphatic hydrocarbon group in the side chain, forexample, 1,2-polybutadiene, can be suitably used as a polymer having anepoxy group. Such partial oxide includes an epoxy group generated byoxidizing an unsaturated bond included in the side chain.

Because of ease of availability, preparation and adjustment of an amountof an epoxy group in the polymer, as the polymer having an epoxy group,a polymer obtained by polymerizing a monomer having an epoxy group or amonomer mixture including a monomer having an epoxy group, and a partiala polymer having an unsaturated aliphatic hydrocarbon group in the sidechain are preferable.

(Monomer Having Epoxy Group or Monomer Mixture Including Monomer HavingEpoxy Group)

Among the polymers having an epoxy group, because of ease ofpreparation, or coating characteristics of a curable composition to abase material, or the like, a homopolymer of a (meth)acrylic acid esterhaving an epoxy group, or a copolymer of a (meth)acrylic acid esterhaving an epoxy group and other monomers is preferable.

The (meth)acrylic acid ester having an epoxy group may be either a chainaliphatic (meth)acrylic acid ester having an epoxy group, or thebelow-mentioned (meth)acrylic acid ester having an alicyclic epoxygroup. Furthermore, the (meth)acrylic acid ester having an epoxy groupmay have an aromatic group. From the viewpoint of transparency of acured product formed using a curable composition, the (meth)acrylic acidester having an epoxy group is preferably an aliphatic (meth)acrylicacid ester having a chain aliphatic epoxy group or an aliphatic(meth)acrylic acid ester having an alicyclic epoxy group, and morepreferably an aliphatic (meth)acrylic acid ester having an alicyclicepoxy group.

Examples of the (meth)acrylic acid ester, which has an aromatic groupand an epoxy group, include 4-glycidyloxyphenyl (meth)acrylate,3-glycidyloxyphenyl (meth)acrylate, 2-glycidyloxyphenyl (meth)acrylate,4-glycidyloxyphenylmethyl (meth)acrylate, 3-glycidyloxyphenylmethyl(meth)acrylate, and 2-glycidyloxyphenylmethyl (meth)acrylate.

Examples of the aliphatic (meth)acrylic acid ester having a chainaliphatic epoxy group include (meth)acrylic acid esters in which a chainaliphatic epoxy group is combined with an oxy group (—O—) in an estergroup (—O—CO—), such as epoxyalkyl (meth)acrylate and epoxyalkyloxyalkyl(meth)acrylate. Such a chain aliphatic epoxy group possessed by the(meth)acrylic acid ester may have one or plural oxy group(s) (—O—) in achain. The number of carbon atoms of the chain aliphatic epoxy group isnot particularly limited, and is preferably 3 or more and 20 or less,more preferably 3 or more and 15 or less, and particularly preferably 3or more and 10 or less.

Specific examples of the aliphatic (meth)acrylic acid ester having achain aliphatic epoxy group include epoxyalkyl (meth)acrylates such asglycidyl (meth)acrylate, 2-methyl glycidyl (meth)acrylate,3,4-epoxybutyl (meth)acrylate, and 6,7-epoxyheptyl (meth)acrylate; andepoxyalkyloxyalkyl (meth)acrylates such as 2-glycidyloxyethyl(meth)acrylate, 3-glycidyloxy-n-propyl (meth)acrylate,4-glycidyloxy-n-butyl (meth)acrylate, 5-glycidyloxy-n-hexyl(meth)acrylate, and 6-glycidyloxy-n-hexyl (meth)acrylate. The curedproduct obtained by curing the above-mentioned curable composition canbe used as protective films for electronic components, such as a liquidcrystal display element, an integrated circuit element, a solid-stateimage sensing device, and the like, an interlayer insulating film, aflat film, and an insulating film. When the cured product is a film, thethickness is preferably 10 nm or more and 100 μm or less, morepreferably 50 nm or more and 10 μm or less, and further preferably 100nm or more and 5000 nm or less.

<<Method for Producing a Compound Represented by the Above Formula (1)>>

A third aspect is a method for producing a compound represented by theabove formula (1) of the first aspect, the method including producingthe compound represented by the above formula (1) by neutralizing thecompound represented by the formula (10) and a base capable of formingan m-valent counter cation X^(m+) in the presence or absence of asolvent.

(In the formula (10), R¹, R², R³, and n are the same as those in theformula (1), and specific examples and preferable examples thereof arethe same.) The base capable of forming an m-valent counter cation X^(m+)is preferably an acyclic or cyclic nitrogen-containing aliphaticcompound, a nitrogen-containing aromatic compound, or a metal atom or anatomic group including the metal atom. It is preferable that the basecapable of forming an m-valent counter cation X^(m+) is a base capableof forming an acyclic or cyclic nitrogen-containing aliphatic cationrepresented by any one of the above formulae (2) to (4), anitrogen-containing aromatic cation represented by any one of the aboveformulae (5) to (13), a nitrogen-containing aliphatic cation representedby any one of the above formulae (14) to (16), or a cation of atomicgroup including a metal element selected from the group consisting of atypical metal element, a transition metal element and a semimetalelement.

Examples of the method for neutralizing the compound represented by theabove formula (10) and the above base in a solvent include a method ofmixing the compound represented by the above formula (10) and the abovebase in, for example, a polar solvent, under heating or without heating.Examples of the above polar solvent include alcohol, and specificexamples include methanol, ethanol, propanol, isopropanol, butanol,tert-butanol, and the like. Under heating, the compound represented bythe above formula (10) and the above base can be dissolved in the abovesolvent and mixed. Heating temperature is, for example, 40° C. or more,preferably 50° C. or more, and more preferably 55° C. or more. The upperlimit of the temperature at the time of heating is not particularlylimited, but, preferably, it is a temperature of a boiling point or lessof the above solvent. Without heating, the compound represented by theabove formula (10) or the above base may not be easily dissolved in asolvent. In this case, as a salt formation proceeds, an amount ofinsoluble matter in the reaction solution can be reduced.

A method for neutralizing a compound represented by the above formula(10) and the above base in the absence of a solvent is not particularlylimited as long as the method is capable of bringing the compoundrepresented by the above formula (10) and the above base into contactwith each other. Specific examples of methods include a method of mixingwhile pulverizing or grinding down the solid compound represented by theabove formula (10) and the solid or liquid base mentioned above in amortar and the like at an ordinary temperature.

Furthermore, the ratio (molar ratio) of the compound represented by theabove formula (10) and the above base is not particularly limited, but avalue of M1/(M2/m) is preferably 20/80 to 80/20, and more preferably30/70 to 70/30 where M1 denotes the number of moles of the compoundrepresented by the formula (10) and M2 denotes the number of moles ofthe above base giving the m-valent counter cation X^(m+).

Furthermore, when a compound represented by the above formula (1)wherein X^(m+) is a sodium cation and a potassium cation, and a basecapable of forming an m-valent counter cation X^(m+) other than thesodium cation and the potassium are mixed with each other to carry outsalt replacement, it is possible to manufacture a compound representedby the above formula (1) in which X^(m+) is cations other than a sodiumcation and a potassium cation.

EXAMPLES

Hereinafter, the present invention will be described more detail basedon the Examples. The present invention is not limited to these Examples.

[Synthesis Example 1] Synthesis 1 of a Compound Represented by the AboveFormula (1)

Compound A (2.00 g, 8.12 mmol) and methanol (20 g) were added into a 50ml three-necked flask. The inside of the flask was subjected toreplacement by nitrogen, followed by heating in a water bath at 60° C.to dissolve the compound A. Next, diazabicycloundecene (DBU; 1.24 g,8.12 mmol) was dropped, and reacted at 60° C. for four hours accordingto the above scheme. After completion of the reaction, the reactedproduct was cooled to room temperature (25° C.). Then, the solvent wasremoved by evaporation from the reaction solution using a rotaryevaporator to obtain a compound represented by the above formula (1)(compound 1). (produced amount=3.27 g, yield=95%, yellow viscous liquid)

¹H-NMR (heavy DMSO, 400 MHz): cation δ (ppm)=3.48 (CH₂, 2H), 3.40 (CH₂,2H), 3.15 (CH₂, 2H), 2.65 (CH₂, 2H), 1.82 (CH₂, 2H), 1.70-1.45 (CH₂,6H),

Anion δ (ppm)=7.70 (CH, 1H), 7.22 (Ph, 2H), 7.15 (CH, 1H), 6.85 (Ph,2H), 6.80 (CH, 1H), 5.63 (CH, 1H), 3.70 (CH₃, 3H), 2.85-2.65 (CH₂, 2H)

[Synthesis Example 2] Synthesis 2 of a Compound Represented by the AboveFormula (1)

Compound A (2.00 g, 8.12 mmol) and methanol (20 g) were added into a 50ml three-necked flask. The inside of the flask was subjected toreplacement by nitrogen, followed by heating in a water bath at 60° C.to dissolve the compound A. Next, diazabicyclononene (DBN; 1.11 g, 8.12mmol) was dropped, and the compound A and DBN were reacted with eachother at 60° C. for four hours according to the above scheme. Aftercompletion of the reaction, the reaction solution was cooled to roomtemperature. Then, the solvent was removed by evaporation from thereaction solution using a rotary evaporator to obtain a compoundrepresented by the above formula (1) (compound 2). (produced amount=2.91g, yield=90%, yellow viscous liquid)

¹H-NMR (heavy DMSO, 400 MHz): cation δ (ppm)=3.55 (CH₂, 2H), 3.40-3.25(CH₂, 4H), 2.81 (CH₂, 2H), 2.00 (CH₂, 2H), 1.88 (CH₂, 2H)

Anion δ (ppm)=7.70 (CH, 1H), 7.22 (Ph, 2H), 7.15 (CH, 1H), 6.85 (Ph,2H), 6.80 (CH, 1H), 5.63 (CH, 1H), 3.70 (CH₃, 3H), 2.85-2.65 (CH₂, 2H)

[Synthesis Example 3] Synthesis 3 of a Compound Represented by the AboveFormula (1)

Compound A (2.00 g, 8.12 mmol) and methanol (20 g) were added into a 50ml three-necked flask. The inside of the flask was subjected toreplacement by nitrogen, followed by heating in a water bath at 60° C.to dissolve the compound A. Next, imidazole (IM; 0.55 g, 8.12 mmol) wasadded, and the compound A and IM were reacted with each other at 60° C.for four hours. After completion of the reaction, the reaction solutionwas cooled to room temperature. Then, the solvent was removed byevaporation from the reaction solution using a rotary evaporator toobtain a compound represented by the above formula (1) (compound 3).(produced amount=2.43 g, yield=95%, white solid)

¹H-NMR (heavy DMSO, 400 MHz): cation δ (ppm)=7.03 (CH, 2H), 7.65 (CH,1H)

Anion δ (ppm)=7.86 (CH, 1H), 7.35 (3H), 6.99 (3H), 5.70 (CH, 1H), 3.71(CH₃, 3H), 3.35-3.16 (CH₂, 2H)

Compound A simple substance and an imidazole simple substance as rawmaterials, and the obtained compound 3 were subjected to measurement ofX-ray diffraction patterns using an X-ray diffraction measuring device(manufactured by Rigaku Corporation; product name “Fully automatichorizontal multi-objective X-ray diffractometer SmartLab”) in thefollowing conditions. Since the obtained compound 3 showed a reflectionpattern different from both of the raw material simple substances, itwas decided that the compound 3 be not a mere mixture but a salt.

X-ray used: CuKα ray derived from rotating anticathode-type X-raygenerator, 45 kV-200 mA

Scanning rate (2θ): 4.0°/min

Divergence slit: (⅔°)

Scattering slit: (⅔°)

Other conditions are standard conditions settings for packagemeasurements “Generic Measurement>Generic (concentration method)”

[Synthesis Example 4] Synthesis 4 of a Compound Represented by the AboveFormula (1)

Compound A (1.60 g, 6.50 mmol) and tetrahydrofuran (3 g) were added intoa 20 ml eggplant flask. The inside of the eggplant flask was subjectedto replacement by nitrogen, followed by heating in an oil bath at 60° C.to dissolve the compound A in tetrahydrofuran. Next,7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD; 1.00 g, 6.50 mmol)was dropped, and compound A and MTBD were reacted at 60° C. for 30minutes according to the above scheme. After completion of the reaction,the reaction solution was cooled to room temperature. Then, the solventwas removed by evaporation from the reaction solution using a rotaryevaporator to obtain a compound represented by the above formula (1)(compound 4). (produced amount=2.5 g, yield=95%, yellow viscous liquid)

¹H-NMR (heavy DMSO, 500 MHz): cation δ (ppm)=9.20 (NH, 1H), 3.27-3.22(6H), 3.17-3.15 (2H), 2.90 (CH₃, 3H), 1.92-1.89 (2H), 1.81-1.79 (2H)

Anion δ (ppm)=7.67 (CH, 1H), 7.21 (2H), 7.12 (1H), 6.84 (2H), 6.79 (1H),5.62 (CH, 1H), 3.71 (CH₃, 3H), 2.73-2.61 (CH₂, 2H)

[Synthesis Example 5] Synthesis 5 of a Compound Represented by the AboveFormula (1)

Compound A (1.50 g, 6.09 mmol) and methanol (9 g) were added into a 20ml eggplant flask. The eggplant flask was subjected to replacement bynitrogen, followed by heating in an oil bath at 60° C. to dissolve thecompound A in methanol. Next, 1,5,7-triazabicyclo[4,4,0]dac-5-ene (TBD;0.85 g, 6.09 mmol) was dropped, and the compound A and TBD were reactedat 60° C. for 30 minutes according to the above scheme. After completionof the reaction, the reaction solution was cooled to room temperature.Then, the solvent was removed by evaporation from the reaction solutionusing a rotary evaporator to obtain a compound represented by the aboveformula (1) (compound 5). (produced amount=2.2 g, yield=95%, yellowsolid)

¹H-NMR (heavy DMSO, 500 MHz): cation δ (ppm)=10.48 (NH, 2H), 3.22-3.17(4H), 3.10-3.07 (4H), 1.86-1.81 (4H)

Anion δ (ppm)=7.71 (CH, 1H), 7.25 (2H), 7.17 (1H), 6.86 (2H), 6.80 (1H),5.65 (CH, 1H), 3.71 (CH₃, 3H), 2.87-2.73 (CH₂, 2H)

[Synthesis Example 6] Synthesis 6 of a Compound Represented by the AboveFormula (1)

Compound A (1.50 g, 6.09 mmol) and methanol (9 g) were added into a 20ml eggplant flask. The inside of the eggplant flask was subjected toreplacement by nitrogen, followed by heating by an oil bath at 60° C. todissolve the compound A in methanol. Next, 1,1,3,3-tetramethylguanidine(TMG; 0.7 g, 6.09 mmol) was dropped, and the compound A and TMG werereacted with each other at 60° C. for 30 minutes according to the abovescheme. After completion of the reaction, the reaction solution wascooled to room temperature. Then, the solvent was removed by evaporationfrom the reaction solution using a rotary evaporator to obtain acompound represented by the above formula (1) (compound 6). (producedamount=2.2 g, yield=100%, yellow solid)

¹H-NMR (heavy DMSO, 500 MHz): cation δ (ppm)=2.84 (6H) Anion δ(ppm)=7.67 (CH, 1H), 7.21 (2H), 7.12 (1H), 6.85 (2H), 6.79 (1H), 5.62(CH, 1H), 3.71 (CH₃, 3H), 2.28-2.64 (CH₂, 2H)

[Synthesis Example 7] Synthesis 7 of a Compound Represented by the AboveFormula (1)

Compound A (1.00 g, 4.06 mmol) and methanol (9 g) were added into a 20ml eggplant flask. The inside of the eggplant flask was subjected toreplacement by nitrogen, followed by heating in an oil bath at 60° C. todissolve the compound A in methanol. Next,imino-tris(dimethylamino)phosphorane (0.72 g, 4.06 mmol) was dropped andthe compound A and imino-tris(dimethylamino)phosphorane were reacted at60° C. for 30 minutes according to the above scheme. After completion ofthe reaction, the reaction solution was cooled to room temperature.Then, the solvent was removed by evaporation from the reaction solutionusing a rotary evaporator to obtain a compound represented by the aboveformula (1) (compound 7). (produced amount=1.7 g, yield=98%, yellowsolid)

¹H-NMR (heavy DMSO, 500 MHz): cation δ (ppm)=2.63 (9H), 2.61, 9H),

anion δ (ppm)=7.65 (CH, 1H), 7.18 (2H), 7.10 (1H), 6.84 (2H), 6.84 (1H),5.61 (CH, 1H), 3.71 (CH₃, 3H), 2.28-2.64 (CH₂, 2H)

[Preparation of Composition]

The following epoxy compound, the compound represented by the formula(1), and the comparative compound were mixed in the blending ratio(parts by mass) shown in the following Table 1 to prepare thecompositions of Example 1 and Comparative Example 1.

TABLE 1 Epoxy compound Compound (part by mass) (part by mass) Example 1The following Compound 3 epoxy compound (5) (95) Comparative Thefollowing Comparative Example 1 epoxy compound compound (95) (5)

[Heat Resistance Evaluation]

The compositions of Example 1 and Comparative Example 1 were evaluatedfor heat resistance. The compositions of Example 1 and ComparativeExample 1 were applied to a glass substrate and heated at 200° C. (fiveminutes) to obtain a cured film having a film thickness of 1 μm. Theobtained cured film was cooled to room temperature once, and thetemperature was increased from room temperature to 200° C. again, andthe state of the film was verified. The cured film of ComparativeExample 1 started to melt around 140° C., but the cured film of Example1 did not melt. Also, the endothermic peak did not appear in observationusing a differential scanning calorimeter (product name: DSC-50,manufactured by Shimadzu Corporation). Therefore, it is considered thata cured film having excellent heat resistance has been obtained.

The invention claimed is:
 1. A compound represented by the followingformula (1):

wherein X^(m+) represents an m-valent counter cation; R¹ represents anoptionally substituted aromatic group; R² represents an optionallysubstituted alkylene group; R³ represents a halogen atom, a hydroxylgroup, a mercapto group, a sulfide group, a silyl group, a silanolgroup, a nitro group, a nitroso group, a sulfonate group, a phosphinogroup, a phosphinyl group, a phosphonate group, or an organic group; mis an integer of 1 or more; n is an integer of 0 or more and 3 or less;and R² may be bonded to R¹ to form a cyclic structure wherein them-valent counter cation X^(m+) is acyclic or cyclic nitrogen-containingaliphatic cation, or a nitrogen-containing aromatic cation, and whereinthe acyclic nitrogen-containing aliphatic cation is selected from thegroup consisting of the following three cations:


2. A method of using the compound according to claim 1 as an epoxycuring catalyst, the method comprising curing an epoxy compound in thepresence of the compound according to claim
 1. 3. A method for producingthe compound according to claim 1, the method comprising: producing thecompound represented by the formula (1) by neutralizing the compoundrepresented by the formula (10) and a base capable of forming anm-valent counter cation X^(m+) in presence or absence of a solvent,

wherein, in the formula (10), R¹ is an optionally substituted aromaticgroup; R² is an optionally substituted alkylene group; R³ is a halogenatom, a hydroxyl group, a mercapto group, a sulfide group, a silylgroup, a silanol group, a nitro group, a nitroso group, a sulfonategroup, a phosphino group, a phosphinyl group, a phosphonate group, or anorganic group; n is an integer of 0 or more and 3 or less; and R² may bebonded to R¹ to form a cyclic structure.
 4. The method according toclaim 3, wherein the base capable of forming the m-valent counter cationX^(m+) is an acyclic or cyclic nitrogen-containing aliphatic compound,or a nitrogen-containing aromatic compound.